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United States Patent |
5,252,247
|
Greco
,   et al.
|
October 12, 1993
|
Metal (dialkylaminoalcoholate) solutions
Abstract
Solubilized metal (dialkylaminoalcoholate) compounds in organic solvent can
serve as a source of metal values for metal oxide-containing
superconductor compositions. Stable solutions, resistant to precipitation
problems, can be formed by reaction of a dialkylaminoalkanol with a metal
alkoxide followed by removal of by-product alkanol by vacuum distillation
below the reflux temperature of the solution. Exemplary metals include
copper, yttrium, barium, calcium, and bismuth, lanthanum and strontium.
Inventors:
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Greco; Carl C. (Garnerville, NY);
Burk; Johst H. (Mohegan Lake, NY)
|
Assignee:
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Akzo America Inc. (Dobbs Ferry, NY)
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Appl. No.:
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668533 |
Filed:
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March 13, 1991 |
Current U.S. Class: |
252/182.12; 534/15; 556/76 |
Intern'l Class: |
C09K 003/00 |
Field of Search: |
252/182.12
534/15
556/76
|
References Cited
U.S. Patent Documents
1990442 | Feb., 1935 | Traube et al. | 556/76.
|
2446682 | Aug., 1946 | Whitner | 556/113.
|
3094546 | Jun., 1963 | Towers | 534/15.
|
3278571 | Oct., 1966 | Mazdiyasni et al. | 534/15.
|
3356703 | Dec., 1967 | Mazdiyasni et al. | 534/15.
|
3479381 | Nov., 1969 | Mitchell | 534/15.
|
3757412 | Sep., 1973 | Mazdiyasni et al. | 534/15.
|
3932545 | Jan., 1976 | Screttas | 502/155.
|
4264370 | Apr., 1981 | Turner | 106/264.
|
4287131 | Sep., 1981 | Langer | 556/174.
|
4489000 | Dec., 1984 | Gradeff et al. | 534/15.
|
4507245 | Mar., 1985 | Ozaki et al. | 534/25.
|
4670573 | Jun., 1987 | Greco et al. | 556/182.
|
4764357 | Aug., 1988 | Sherif et al. | 423/338.
|
4801692 | Jan., 1989 | Gradeff et al. | 534/15.
|
4837190 | Jun., 1989 | Summers et al. | 534/15.
|
4839339 | Jun., 1989 | Bunker et al. | 505/1.
|
4847239 | Jul., 1989 | Piotrowski et al. | 505/801.
|
4900536 | Feb., 1990 | Snyder et al. | 423/593.
|
4920093 | Apr., 1990 | Nonaka et al. | 505/1.
|
5021395 | Jun., 1991 | Druliner et al. | 505/1.
|
5024991 | Jun., 1991 | Tsunashima et al. | 505/1.
|
5028667 | Jul., 1991 | McLain et al. | 525/415.
|
5099006 | Mar., 1992 | Gradeff et al. | 534/15.
|
5106828 | Apr., 1992 | Bhargava et al. | 505/1.
|
Foreign Patent Documents |
62-240691 | Oct., 1987 | JP.
| |
84/01045 | Jan., 1985 | WO.
| |
712828 | Aug., 1954 | GB | 556/76.
|
1188974 | Apr., 1970 | GB.
| |
Other References
Wheeler et al., J. Am. Pharm. Assoc., Sci. Ed., XXXIII, No. 5, 156-158 (May
1949) "Dihydroxypropyl Bismuthale".
Ojima et al, Zeitschrift fur Anorganische und Allgemeine Chemie, 309
(1961), pp. 110-120.
Hein et al., Z. fur Anorganische Allgemeine Chemie, 282 (1955), pp. 93-209.
Smolander, Inorg. Chim. Acta., 128 (1), pp. 61-63 (1987).
|
Primary Examiner: Miller; Edward A.
Attorney, Agent or Firm: Fennelly; Richard P., Morris; Louis A.
Parent Case Text
This is a continuation of application Ser. No. 270,570 filed Nov. 14, 1988,
now abandoned.
Claims
We claim:
1. A solution which consists essentially of: (a) an organic solvent; and
(b) a metal (dialkylaminoalcoholate) compound dissolved therein, the metal
being a metal oxide superconductor precursor selected from the group
consisting of yttrium, bismuth, and lanthanum.
2. A solution as claimed in claim 1 wherein the metal is yttrium.
3. A solution as claimed in claim 1 wherein the metal is bismuth.
4. A solution as claimed in claim 1 wherein the metal is lanthanum.
Description
BACKGROUND OF THE PRESENT INVENTION
1. Field of the Invention
The present invention relates to metal (dialkylaminoalcoholate) solutions
which can serve, for example, as a source of metal for the manufacture of
metal oxide superconductor compositions.
2. Description of the Prior Art
There is currently much interest in high T.sub.c superconductor
compositions which are metal oxides. Representative metal components in
such compositions include: copper, yttrium, barium, calcium, bismuth,
lanthanum, strontium, and the like. These metal moieties are termed "metal
oxide superconductor precursor" metals in accordance with the present
invention which is directed to certain novel compounds containing such
precursor moieties, solutions containing them which find use in
conjunction with chemical means to form the ultimately desired
superconductor metal oxide composition, and to certain processes for
forming the compounds and solutions.
The prior art description of the copper complexes of dialkylaminoalcoholate
solutions, for example, appears to focus on aqueous solutions. For
example, U.S. Pat. No. 2,446,682 mentions their use to modify cellulose
textiles and names diethylethanolamine (Col. 7, line 38) and
methyldiethanolamine (Col. 7, line 41) as representative alkylolamines
which can be used. Ojima et al. in Z. fur Anorganische und Allgemeine
Chemie, Band 309 (1961) pp. 110-120 mentions (on pages 110-111) that the
state of knowledge about the structure and properties of copper complexes
of ethanolamine and its derivatives formed in aqueous solution seemed to
be "limited" at the time of their work. Ojima et al. cited earlier work by
Hein et al. (Z. Anorg. Allg. Chem., 282, 93 (1955) in regard to their
review of the prior art. Hein et al. only show halide-containing
complexes. There is no showing or suggestion of organic solvent/alkoxide
compositions or their use in making metal oxide superconductor
compositions.
The prior art description of calcium alkoxides also appears to be devoid of
the novel calcium (dialkylaminoalcoholates) of the instant invention. U.S.
Pat. No. 4,287,131 indicates, at Col. 1, lines 52-55, that certain metal
alkoxide derivatives of C.sub.1 -C.sub.10 alkanolamines can be formed
without a clear suggestion that a dialkyl moiety "Z" is to be chosen. No
exemplification of any calcium (dialkylaminoalcoholate) appears in this
patent. International Patent Publication No. WO 85/00365 mentions the
possibility of contacting CaO or CaOH with an "activator" and names
N-methylethanolamine, a monoalkyl-substituted amine compound, on page 31
thereof (last one). Finally, British Patent No. 1,188,974 indicates (page
3, lines 40 et seq.) formation of metal alcoholates from amino alcohols.
It exemplifies a calcium (dialkoxyalkylaminoalcoholate in Example 34 and a
calcium (dialkylaminoalcoholate) having oxygen atom interruption in its
alkylene moiety in Example 52.
SUMMARY OF THE PRESENT INVENTION
The present invention relates to organic solutions containing a soluble
metal alkoxide (i.e., a metal (dialkylaminoalcoholate)) which can serve as
a stable and convenient source of metal, e.g., for use in making metal
oxide-containing superconductor compositions. The metal
(dialkylaminoalcoholate) compositions of the present invention are
essentially halide-free. The instant invention also relates to certain
novel metal (dialkylaminoalcoholate) compounds and to certain novel
processes for forming the solutions.
DETAILED DESCRIPTION OF THE PRESENT INVENTION
It is highly desirable to be able to produce organic solutions containing
solubilized metal alkoxides. Such solutions can serve as a source of the
metal for a metal oxide superconductor composition. The presence of the
solubilized metal alkoxide makes it much easier for the person of ordinary
skill in the art to measure more accurately the available metal values for
combination with other solubilized metal alkoxides in making metal oxide
superconductors. However, it has been difficult heretofore to obtain
soluble solutions of the desired metal alkoxides which possessed good
storage stability. They would have a tendency to precipitate metal values
from solution, thereby rendering it difficult to give an accurate measure
of the available (solubilized) metal values still in solution.
The present invention relates to solubilized metal dialkylaminoalcoholate
compounds which have good storage stability. These compounds are of the
formula M(ORNR'.sub.2).sub.2 where M is a superconductor metal precursor,
R is alkylene of from 2 to 3 carbon atoms and R' is alkyl of from 1 to 8
carbon atoms, with the proviso that if R' is straight chain, the number of
carbon atoms in the straight chain is no more than 3. Preferred ligand
systems are those which can form 5- or 6-membered rings with the central
metal atom via internal coordination between the nitrogen atom on the
ligand and the metal atom. Examples of suitable metal precursors for the
metal oxide superconductor include copper, yttrium, barium, calcium,
bismuth, lanthanum, strontium and the like.
Depending upon the reactivity between the metal moiety desired and the
dialkylaminoalcohol of choice, the reaction for forming the desired
compounds can be conducted from either the metal per se or a metal
alkoxide. It has been found that the metal per se can be used in cases
where the superconductor metal precursor is calcium, barium or strontium,
preferably by ball milling the metal to activate it as described in U.S.
Pat. No. 4,670,573. When the metal moiety is the more non-reactive copper,
bismuth or yttrium, for example, an appropriate conventional metal
alkoxide thereof is the desired starting material for reaction with the
selected dialkylaminoalcohol.
The compounds described above can be easily formed by a two-step procedure
when the metal alkoxide is the desired reagent. The first stage can
involve the formation of a metal alkoxide by reaction of a metal salt
(e.g., a copper halide such as cupric chloride) with an alkali metal
alcoholate (such as lithium methoxide). The alkali metal alcoholate is
formed by reaction between an alcohol and molten alkali metal. This
reaction is conducted in a, solvent medium, most preferably the alcohol
chosen for reaction with the alkali metal. The metal alkoxide that is
formed can be freed of impurities by washing with the alcohol.
Once the metal alkoxide has been formed it can be suspended in a solvent
(such as toluene, trimethylbenzene, or the like) and reacted with a
dialkylaminoalkanol. This reaction forms the desired metal
(dialkylaminoalcoholate) compounds and alcohol by-product. The alcohol
by-product, if removed by vacuum distillation at temperatures below the
reflux temperature (e.g., about 35.degree.-50.degree. C.), will enable the
production of a solution of the dialkylaminoalcoholate which has good
resistance to precipitation problems.
The present invention is further understood by reference to the Examples
which follow.
EXAMPLE 1
In 600 cc of methanol was dissolved 34 grams of copper(II) chloride (0.253
mole). To this solution was added 5 grams of lithium (0.725 mole). The
solution was stirred for four hours at room temperature. At the end of
this time there was formation of a blue solid precipitate (copper
methoxide). The precipitate was filtered from the reaction mixture and was
washed four times. with 250 cc of methanol each time to remove LiCl and
unreacted copper chloride. The blue solid was vacuum dried in the vacuum
oven at 40.degree. C. under nitrogen, and was then suspended in 400 cc of
toluene. To this slurry was added 86 grams (0.76 mole) of
diethylaminoethanol over a 10 minute period. The reaction mixture was
heated to 35.degree. C. under a vacuum of 25 mm of mercury for 45 minutes
to remove the methanol. About 100 cc of methanol-toluene was distilled off
during this time, keeping the pot temperature below 40.degree. C. A clear
dark blue solution resulted after the heating period and was diluted with
more toluene to arrive at a final weight of 668 grams. The amount of
copper alkoxide, of the formula Cu(OCH.sub.2 CH.sub.2 N(Et).sub.2).sub.2,
in this solution was 74.8 grams or 11.2% by weight.
The material was stored in a dry box for several weeks with no evidence of
any precipitation. A portion of this material was mixed with a solution of
barium diethylaminoethoxide and allowed to stand at room temperature under
nitrogen. This solution was also stable for many weeks. No sign of
precipitation was noted.
EXAMPLE 2
The same procedure described in Example 1 was used with the exception that
dimethylaminoethanol was used as the alcoholic ligand in the preparation
of the copper/barium alkoxide mixture wherein the copper compound had the
formula Cu(OCH.sub.2 CH.sub.2 N(Me).sub.2).sub.2. Similarly, no
precipitation was observed for the resulting solution after several weeks.
EXAMPLE 3
To a one liter flask was added 100 grams of the copper alkoxide solution
from Example 1 (the solution was analyzed for copper and found to contain
2.52% Cu). While under a nitrogen atmosphere, there was added 77 grams of
a barium diethylaminoethylate solution. This solution was analyzed and
found to contain 4.7% barium. The above solution was then mixed with 26
grams of a yttrium diethylaminoethylate solution containing 4.6% yttrium.
The resulting solutions were stirred at room temperature for one hour and
then allowed to stand at room temperature for an infinite period of time.
After two months standing, no sign of precipitation was noted.
COMPARATIVE EXAMPLE 4
To 800 cc of methanol was added 40 grams of copper(II) chloride (0.297
mole) which produced a green colored solution. To this solution was then
added 38.4 grams of butyl lithium (0.6 mole) in hexane over a 30 minute
period. The temperature rose to 50.degree. C. and a blue precipitate
formed. The reaction mixture was stirred for six hours at room
temperature. The reaction mixture was filtered and the precipitate (copper
methoxide) was suspended in toluene and was distilled to dryness at
80.degree. C./60 mm of Hg. The solid that remained was redissolved in
toluene and was reacted with more butyl lithium to insure all of the
copper chloride had reacted. The reaction mixture was filtered again, and
the precipitate was washed three times with 150 cc of methanol. The
precipitate was vacuum dried and was again suspended in toluene (500 cc).
To this slurry was then added 59 grams of dimethylaminoethanol (0.6 mole
plus 10% excess). The reaction was heated to reflux (about 64.degree. C.)
and the methanol azeotroped with the toluene. It took two hours to remove
all traces of methanol from the solution. The solution that remained was a
dark navy blue color and was filtered at room temperature. The filtrate
was allowed to stand at room temperature under nitrogen. The next day a
great deal of solids had come out of solution. After a week, more solids
came out of solution.
EXAMPLE 5
This Example illustrates the preparation of a mixed solution of yttrium,
barium and copper diethylaminoethoxide.
A solution of 60 grams of yttrium diethylaminoethoxide in toluene (4.6% Y)
was mixed with a solution of barium diethylaminoethoxide (23 grams) in
mesitylene. The mesitylene-barium solution weighed 181 grams. The
resulting solution weighed 241 grams. This clear-yellow solution was
stripped to a weight of 51.6 grams [23 grams of Ba(OCH.sub.2 CH.sub.2
NEt.sub.2).sub.2 and 13.5 grams of Y(OCH.sub.2 CH.sub.2 NEt.sub.2).sub.3
in solution].
To the above solution was then added 227 grams of a copper
diethylaminoethoxide-mesitylene solution containing 2.6% copper. The
resulting dark blue solution was stirred at 40.degree.-50.degree. C for
one hour. The solution by analysis contained 0.031 mole of the yttrium
alkoxide, 0.062 mole of the barium alkoxide and 0.093 mole of the copper
alkoxide. This solution was storage stable for over two months with no
sign of precipitation. The solution comprised around a 22% concentration
of the metal alkoxides.
EXAMPLE 6
This Example illustrates preparation of barium diethylaminoethoxide
solution.
In a 1-L, 3-neck flask was added 22 grams of barium metal (0.16 mole) into
400 cc of trimethylbenzene or mesitylene. To this solution was added 56
grams of diethylaminoethanol (0.48 mole) over a 10 minute period. The
reaction mixture was heated to reflux where hydrogen started to evolve.
The reaction mixture was refluxed for three hours during which hydrogen
was continually coming from the reaction. Then the mixture was cooled and
filtered. The filtrate, a yellow-orange solution, weighed 458 grams. This
filtrate was analyzed and found to contain 4.7% barium which corresponds
to 57.9 grams of the desired alkoxide (98% yield).
EXAMPLE 7
This Example illustrates the preparation of a calcium diethylaminoethoxide
solution.
Same procedure as above in Example 6 except that 14.5 grams of calcium
(0.36 mole), which had been premilled with a catalytic amount (about 0.1
gm/25 gm of calcium) of mercury chloride, was used in 500 cc of toluene.
To this was added 126 grams of diethylaminoethanol (1.1 moles). Hydrogen
was given off during a 24 hour reflux period. The filtrate weighed 624
grams. Analysis showed that the filtrate contained 1.5% calcium (9.36
grams). The yield was 65% of the desired calcium diethylaminoethylate
based on the calcium analysis.
EXAMPLE 8
This illustrates preparation of a bismuth diethylaminoethoxide solution.
In a 1-L, 3-neck flask was added 20 grams of bismuth methoxide (0.066
mole). To this, under N.sub.2, was then added 400 cc of mesitylene and 100
cc of toluene. The reaction was equipped with a Dean-Stark apparatus.
Dimethylaminoethanol (17.8 grams, 0.2 mole) was added, and the reaction
was heated to reflux. During the reflux period 120 cc of a
toluene-methanol mixture was azeotroped off over a two hour period. Most
of the bismuth methoxide had gone into solution and reacted. The reaction
mixture was filtered using a CELITE filter cake as the filtering aid. The
filtrate weighed 414 grams and was analyzed to contain 2.5% Bi. According
to the analysis the amount of bismuth diethylaminoethylate formed was 23.4
grams (75% yield).
EXAMPLE 9
In a one liter, three neck flask was suspended 25 grams of lanthanum metal
(0.18 mole) and 0.5 grams of mercury sulfate into 400 cc of toluene. To
this slurry was added 96 grams of diethylaminoethanol (0.82 mole). The
resulting reaction mixture was heated to reflux with vigorous evolution of
hydrogen. The reaction was filtered after refluxing for twelve hours. The
filtrate was distilled to constant weight until an orange-yellow semisolid
remained. It weighed 6.4 gram which represented an 88% yield of the
desired lanthanum diethylaminoethylate. This alkoxide product was
redissolved in toluene to form a stable solution at around 20%
concentration.
The organic solvent solutions containing the subject metal
(dialkylaminoalcoholate) compounds can be used to make metal oxide
superconductor compositions as described before. The first step is to make
a series of solutions (or a mixed solution) of the desired superconductor
metal moieties (e.g., a series of solutions, or a mixed solution of
yttrium, barium and copper dialkylaminoalcoholate compounds). If a mixed
solution is made, the metal moieties are present in the molar ratios
desired in the final superconductor composition. If separate solutions
containing each respective metal moiety are made, they would be combined
in the appropriate ratios to yield the metal moieties in such ratios.
Next, the organic solvent solutions containing these metal
(dialkylaminoalcoholate) compounds are hydrolyzed to form a gel by being
mixed with a mixture of water and an alcohol which is miscible with the
organic solvent (e.g., ethanol, isopropanol or an alkoxy alcohol such as
methoxypropanol). The gel can be isolated by evaporation of the solvent
and then can be fired to dry and fuse it into the desired superconductor
composition.
The foregoing Examples illustrate certain embodiments of the instant
invention but should not be construed in a limiting sense as defining the
scope of protection desired. The claims which follow set forth the scope
of protection desired.
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